m-Formylbenzonitrile → HCID 53256704, compound

HRID 1044825Notes

Reaction equation

HRID 1044825 reaction equation
[CH:1]1([Mg]Br)[CH2:3][CH2:2]1.[CH:6]([C:8]1[CH:9]=[C:10]([CH:13]=[CH:14][CH:15]=1)[C:11]#[N:12])=[O:7]>C1COCC1>[CH:1]1([C:6]([C:8]2[CH:9]=[C:10]([CH:13]=[CH:14][CH:15]=2)[C:11]#[N:12])=[O:7])[CH2:3][CH2:2]1.[CH:1]1([CH:6]([OH:7])[C:8]2[CH:9]=[C:10]([CH:13]=[CH:14][CH:15]=2)[C:11]#[N:12])[CH2:3][CH2:2]1

Participants

5

Reactant 2

HCID 90670m-FormylbenzonitrileHCID 178418630HCID 178418630, compound

Product 2

HCID 247240893-(Cyclopropanecarbonyl)benzonitrileHCID 53256704HCID 53256704, compoundYield 91%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

The key intermediate 3-(Cyclopropanecarbonyl)benzonitrile was prepared as follows; a) Cyclopropylmagnesium bromide (1M in THF, 6 ml, 6 mmol) was added to a solution of 3-formylbenzonitrile in THF (12 ml) at −78° C. and stirred at 0° C. for 5 hours. The reaction was quenched with saturated NH4Cl solution (30 ml), extracted with EtOAc, washed with water (×2) and brine, dried (MgSO4) and evaporated under reduced pressure. The residue was purified by column chromatography on silica (EtOAc/Hexanes 20/80-50/50) to give 3-(cyclopropyl(hydroxy)methyl)benzonitrile (778 mg, 91%). b) 2-Iodoxybenzoic acid (IBX) was added to a solution of 3-(cyclopropyl(hydroxy)methyl)benzonitrile (171 mg, 1 mmol) in EtOAc (5 ml) at room temperature and stirred at 80° C. for 2 hours. After cooling to 0° C., the precipitated materials were filtered off and washed with EtOAc (3 ml×2), then the filtrate was evaporated under reduced pressure. The residue was purified by column chromatography on silica (EtOAc/Hexanes 5/95-30/70) to give 3-(cyclopropanecarbonyl)benzonitrile (225 mg, 100%).

Workup

  1. customThe reaction was quenched with saturated NH4Cl solution (30 ml)
  2. extractionextracted with EtOAc
  3. washwashed with water (×2) and brine
  4. dry with materialdried (MgSO4)
  5. customevaporated under reduced pressure
  6. customThe residue was purified by column chromatography on silica (EtOAc/Hexanes 20/80-50/50)

Sources & evidence

ORD record
ord-9e547a22aa244451a1807df180de1612
Source dataset
uspto-grants-2013_10
Patent number
US08563732B2

Reaction notes

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